CN105016385B - Hydrothermal preparation method of laminar multi-element photoelectric sulfide - Google Patents
Hydrothermal preparation method of laminar multi-element photoelectric sulfide Download PDFInfo
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Abstract
The invention relates to a hydrothermal preparation method of a laminar multi-element photoelectric sulfide. The chemical composition of the multi-element photoelectric sulfide is AQ2MS3, AQMS2, AQM2S6, A2QMS4, A2Q2MS4, A2Q2M2S6, A2QM2S6, A3Q9M4S12, A3Q3M2S8, AQMS3, or A4Q6M3S14, wherein A is any one of Li, Na, K, Rb and Cs; Q is any one of Cr, Mn, Fe, Ni, Cu, Zn, Ag, Cd and Sn; and M is any one of Sb, Bi, Ge, Sn, As, Mn, Nb and W. The preparation method comprises the following steps: uniformly mixing a Q source and an M source in a stoichiometric ratio with excess sulfur source, AOH and water, and then performing hydrothermal reaction in a hydrothermal kettle at 150-250 DEG C for 1-10 days; and separating out a reaction product, washing, centrifuging and drying to prepare the multi-element photoelectric sulfide. Through the insertion of alkali metal ions in reaction raw materials, a compound with a laminar structure is easy to obtain.
Description
Technical field
The invention belongs to novel photoelectric compound-material synthesis field, it is related to a kind of hydro-thermal of stratiform polynary photoelectricity sulfide
Preparation method.
Background technology
With the continuous development of material science, new multicomponent photoelectricity compound-material has become as various countries scientist institute
The important research target of concern.However, how by simply, economically and efficiently method obtains and has the many of excellent physical properties
First photoelectricity compound-material is the premise realizing this important goal.At present, designed by different experiments means and synthesize polynary light
Electric compound material has become as one of focus of people's research.
In photoelectricity compound-material, binary optical electric compound material has been widely studied and has been applied to every field.
However, these materials that constantly improve with science can not fully meet the demand of people.The diversification of material is to enrich it
The natural thinking of property, also complies with human research and the historical development rule of application novel photoelectric compound-material.Follow polynary
Change this thinking, naturally we will recognize that searching and design polynary photoelectricity compound-material, increase further its physics and
The adjustability of chemical property, meets requirement in a particular application, accordingly it is desirable to by the diversification of material Lai further
Realize excellent properties that binary material do not possess to meet human wants.
Sulfide is the important semiconducting compound of a class, these compounds be widely used in solar cell, transistor,
The field such as photo-detector and temperature-sensitive device.From the point of view of sulfide is as the evolution of solar battery obsorbing layer, from binary
Cu2S to the CuInS of ternary2,CuInSe2Or even nearest quaternary compound Cu2ZnSnS4, it can be found that element species are gradually
Increase, that is, multi-element compounds and alloy semiconductor are the directions developed.Not only solar photovoltaic device so, other kinds work(
Can device also develop towards the direction of material diversification.Reason is the multi-element alloyed important channel being to design new material, due to
The increasing of chemical composition and the Degree of Structure Freedom, multicomponent alloy material shows various abundant, unique properties, and significantly having widened should
The range of choice with material.
Such as especially from ternary CuInSe2Become quaternary CuInxGa1-xSe2Alloy, band gap can be by adjusting Ga's and In
Relative components reduce further, to 1.4-1.5eV about, close to the ideal bandgap of unijunction solar cell absorbed layer.However, from
Increased by degree and also imply that property is more complicated, therefore to the property research of multi-element compounds than unit and binary compound
Matter research is more difficult.Except CuInxGa1-xSe2And Cu2ZnSnS4Have outside good photoelectric properties Deng material, CuMS2(M=
Sb, Bi) it is also the important photoelectricity compound of a class, but the research to this kind of photoelectricity compound is little.
Sulfide material can be by solid-phase sintering and liquid phase method synthesis.Solid-phase sintering process needs higher reaction temperature
Degree, and the requirement to experimental facilitiess is higher compared with liquid phase method.Therefore, liquid phase method becomes the important method of sulfide synthesis.In crowd
In many liquid-phase synthesis process, hydro-thermal method, because preparation method is simple, widely should the advantages of required experimental facilitiess are cheap
Preparation for various polynary sulfide semiconductors.
Content of the invention
The problem existing in the face of prior art, it is an object of the invention to provide a kind of hydro-thermal of stratiform polynary photoelectricity sulfide
Preparation method, to obtain the stratiform polynary photoelectricity sulfide of good quality by straightforward procedure, cheap equipment.
Here, the present invention provides a kind of hydrothermal preparing process of stratiform polynary photoelectricity sulfide, described polynary photoelectricity sulfuration
The chemical composition of thing is AQ2MS3、AQMS2、AQM2S6、A2QMS4、A2Q2MS4、A2Q2M2S6、A2QM2S6、A3Q9M4S12、A3Q3M2S8、
AQMS3, or A4Q6M3S14, wherein, A is any one in Li, Na, K, Rb, Cs；Q be Cr, Mn, Fe, Ni, Cu, Zn, Ag, Cd,
Any one in Sn；M is any one in Sb, Bi, Ge, Sn, As, Mn, Nb, W；
Described preparation method includes：
（1）After being mixed homogeneously with excessive sulphur source, AOH and water in the Q source of stoichiometric proportion and M source in water heating kettle in
150～250 DEG C of hydro-thermal reactions 1～10 day；
（2）Isolate product and wash, be centrifuged, drying i.e. prepared described polynary photoelectricity sulfide.
The present invention adopts hydro-thermal method to prepare stratiform polynary photoelectricity sulfide, and preparation method is simple, and required experimental facilitiess are honest and clean
Valency, and it is readily available the compound of metastable phase, in addition, the insertion of the alkali metal ion in reaction raw materials is readily available stratiform knot
Structure compound, and the product quality obtaining is excellent, has the advantages that even grain size, particle diameter be big, good crystallinity.And this
Bright method applies also for the preparation of other polynary laminate sulfides.
It is preferred that step（1）In, described Q source and described sulphur source mole are 1：（2～30）.
It is preferred that step（1）In, described Q source and described AOH are mixed in the ratio that every 1mmol Q source uses 0.1～5gAOH
Close.
It is preferred that step（1）In, described Q source and described water use the ratio mixing of 0.5～5g water in every 1mmol Q source.
It is preferred that step（1）In, the compactedness of water heating kettle is 20～80%.
It is preferred that described Q source is that the hydrochlorate of Q, nitrate, acetate, sulfate, oxide, hydroxide and Q are mono-
At least one in matter.
It is preferred that described M source is that the hydrochlorate of M, nitrate, acetate, sulfate, oxide, hydroxide and M are mono-
At least one in matter.
It is preferred that described sulphur source is in thiourea, sulphur powder, thioacetamide, sodium thiosulfate, sodium sulfide and thiacetic acid.
At least one.
Brief description
Fig. 1 is the stratiform polynary photoelectricity sulfide KCu of the present invention2SbS3Crystal structure figure；
Fig. 2 is the stratiform polynary photoelectricity sulfide KCu of the present invention2SbS3Scanning electron microscope (SEM) photograph；
Fig. 3 is the stratiform polynary photoelectricity sulfide KCu of the present invention2SbS3X-ray diffraction spectrum；
Fig. 4 is the stratiform polynary photoelectricity sulfide AQMS of the present invention2Crystal structure figure；
Fig. 5 is the stratiform polynary photoelectricity sulfide KCuZnS of the present invention2Scanning electron microscope (SEM) photograph；
Fig. 6 is the stratiform polynary photoelectricity sulfide KCuZnS of the present invention2Another scanning electron microscope (SEM) photograph.
Specific embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment it should be appreciated that accompanying drawing and following embodiment
It is merely to illustrate the present invention, and the unrestricted present invention.
The present invention provides a kind of preparation method of stratiform polynary photoelectricity sulfide.In one embodiment, this stratiform is many
The chemical composition of first photoelectricity sulfide is AQ2MS3、AQMS2、AQM2S6、A2QMS4、A2Q2MS4、A2Q2M2S6、A2QM2S6、
A3Q9M4S12、A3Q3M2S8、AQMS3, or A4Q6M3S14, wherein, A is any one in Li, Na, K, Rb, Cs；Q be Cr, Mn,
Any one in Fe, Ni, Cu, Zn, Ag, Cd, Sn；M is any one in Sb, Bi, Ge, Sn, As, Mn, Nb, W.
Specifically, described stratiform polynary photoelectricity sulfide includes but is not limited to：KCu2MS3(M=Sb,Bi)、A2Ag2GeS4,
A2Ag2SnS4,A2Ag2SbS4,A3Ag9Sb4S12,A2Cu2Sn2S6,A2Cu2SnS4,ACu2AsS3,ACuMnS2,A3Cu3Nb2S8,
A4Cu6W3S14,A2CdSbS4,A2MnSbS4,A2ZnSbS4,ACdAsS3,ACrSn2S6,A2NiSn2S6,A2FeSn2S6,A2SnAs2S6,
AAg2AsS3,A3Ag9Sb4S12(A=Li, Na, K, Rb, Cs) etc..
Preparation method preferably adopts hydro-thermal method.Specifically, hydrothermal preparing process may include following steps.
Q source, M source, sulphur source, AOH and water mix homogeneously are formed reaction mixture.Hybrid mode can be for example in room
Temperature stirring 5～20 minutes.Wherein, Q source and M source preferably stoichiometrically add.Sulphur source and/or AOH are preferably with respect to Q
Source and M source are excessive.In one example, Q source and sulphur source mole is 1：（2～30）.In another example, every 1mmol Q
Source uses 0.1～5gAOH.In another example, every 1mmol Q source uses 0.5～5g water.
As Q source, for example, can adopt hydrochlorate, nitrate, acetate, sulfate, oxide, hydroxide and the Q of Q
At least one in simple substance.
As M source, for example, can adopt hydrochlorate, nitrate, acetate, sulfate, oxide, hydroxide and the M of M
At least one in simple substance.
As sulphur source, such as can be using in thiourea, sulphur powder, thioacetamide, sodium thiosulfate, sodium sulfide and thiacetic acid.
At least one.
The reaction mixture being obtained is placed in water heating kettle and carries out hydro-thermal reaction.Hydrothermal temperature can be 150～250
℃.The hydro-thermal reaction time can be 1～10 day.The compactedness of water heating kettle can be 20～80%.
After completion of the reaction, carry out post processing to obtain product.Can be for example to isolate reaction from reactant liquor to produce
Thing, and wash, be centrifuged and dry.Wherein, centrifugation can be centrifuged 3～10 times with 500～3000 revs/min of rotating speed.Dry
Can be to dry in 30～100 DEG C of vacuum drying ovens.
Hereinafter, with KCu2MS3The present invention is described as a example (M=Sb, Bi).
In this example, reactant presoma deionized water, copper powder, antimony (bismuth) powder, thiourea and potassium hydroxide are added successively
Enter in reaction reagent bottle and be stirred at room temperature, put into reaction in baking oven after then reactor being sealed, finally reactant is taken out
The deionized water cleaning product that simultaneously speed centrifugation obtains is placed on to dry in vacuum drying oven and obtains stratiform polynary photoelectricity sulfide
KCu2MS3(M=Sb,Bi).
Specifically, may include steps of：Successively by reactant presoma 4-40ml deionized water, 0.5-50mmol copper
Powder, 0.5-50mmol antimony (bismuth) powder, 10-1000mmol thiourea, 1-30g potassium hydroxide add in the reactor of 10-100ml,
Stir 5-20min under room temperature condition, put into after then reactor being sealed in 150-250 DEG C of baking oven and react 1-10 days；Then
It is centrifuged 3-10 time by reactant taking-up deionized water cleaning and with 500-3000 rev/min of rotating speed, finally true at 30-100 DEG C
The product obtaining is dried in empty baking oven.
In the case that other reaction conditions are constant, in copper powder, antimony (bismuth) powder and three kinds of precursors of thiourea any one or
Two kinds can use other precursors to replace：Described reactant precursor copper powder can use copper chloride, Cu-lyt., copper nitrate, vinegar
Sour copper, the mantoquita such as copper sulfate is replacing；Antimony (bismuth) powder can use Butter of antimony. (bismuth), nitric acid antimony (bismuth), stibium oxide (bismuth), hydrogen-oxygen
Change antimony (bismuth) salt such as antimony (bismuth) to replace；Thiourea can use sulphur powder, thioacetamide, sodium thiosulfate, sodium sulfide, thiacetic acid.
To replace etc. sulphur source.
In the case that other reaction conditions are constant, presoma potassium hydroxide can use Lithium hydrate, sodium hydroxide, hydroxide
The highly basic such as rubidium and Cesium hydrate. replaces preparation ACu2MS3(M=Sb,Bi)(A=Li,Na,Rb,Cs).
In the case that other reaction conditions are constant, the method is also suitable for the preparation of the polynary sulfide of other stratiforms, can profit
Had with the multi-element metal sulfide of the method preparation：A2Ag2GeS4,A2Ag2SnS4,A2Ag2SbS4,A3Ag9Sb4S12,
A2Cu2Sn2S6,A2Cu2SnS4,ACu2AsS3,ACuMnS2,A3Cu3Nb2S8,A4Cu6W3S14,A2CdSbS4,A2MnSbS4,
A2ZnSbS4,ACdAsS3,ACrSn2S6,A2NiSn2S6,A2FeSn2S6,A2SnAs2S6,AAg2AsS3,A3Ag9Sb4S12(A=Li,
Na, K, Rb, Cs) etc., these compounds all can use corresponding simple substance：Ag,Ge,Sn,Sb,As,Mn,Nb,W,Cd,Zn,Cd,Cr,
Ni and thiourea obtain as forerunner's precursor reactant.
Fig. 1 illustrates the stratiform polynary photoelectricity sulfide KCu being obtained by the method for one example of the present invention2SbS3Crystal knot
Composition.Fig. 4 illustrates the stratiform polynary photoelectricity sulfide AQMS that the method for one example of the present invention is obtained2Crystal structure figure.By
Fig. 1 and Fig. 4 understands, due to alkali metal ion（Such as potassium ion）Insertion and easily form lamellar structure compound.Fig. 2 illustrates
The stratiform polynary photoelectricity sulfide KCu being obtained by the method for one example of the present invention2SbS3Scanning electron microscope (SEM) photograph.Fig. 5, Fig. 6 are respectively
The stratiform polynary photoelectricity sulfide KCuZnS that the method for one example of the present invention is obtained is shown2Different multiplying scanning electron microscope
Figure.From Fig. 2, Fig. 5, Fig. 6, the stratiform polynary photoelectricity sulfide even grain size of gained of the present invention, particle diameter are big, crystallinity
Good.Fig. 3 illustrates the stratiform polynary photoelectricity sulfide KCu being obtained by the method for one example of the present invention2SbS3X-ray diffraction spectrum.
As known from the above, it is an advantage of the current invention that：Preparation method is simple, and required experimental facilitiess are cheap, are readily available
The compound of metastable phase, the insertion of alkali metal ion is readily available lamellar structure compound, and the production die size obtaining is equal
Even, big, good crystallinity of particle diameter etc..The experimental technique of this invention applies also for the preparation of other stratiforms polynary photoelectricity sulfide.
Enumerate embodiment further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this
Some nonessential improvement that bright the above is made and adjustment belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only one of OK range example, and that is, those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
Successively by reactant presoma 10ml deionized water, 5mmol copper powder, 5mmol antimony (bismuth) powder, 100mmol thiourea,
15g potassium hydroxide adds in the reactor of 50ml, stirs 10min at ambient temperature, puts into 200 after then sealing reactor
DEG C baking oven in react 3 days；Then reactant is taken out deionized water cleaning and be centrifuged 5 times with 1000 revs/min of rotating speed,
The product obtaining is dried afterwards in 80 DEG C of vacuum drying ovens.KCu in products therefrom2SbS3Crystal structure figure, scanning electron microscope
Figure, X-ray diffraction spectrum are respectively referring to Fig. 1～3.
Embodiment 2
Successively by reactant presoma 4ml deionized water, 8mmol Schweinfurt green, 8mmol Butter of antimony. (bismuth), 160mmol sulfur
Powder, 1g potassium hydroxide add in the reactor of 10ml, stir 5min at ambient temperature, put into after then sealing reactor
React 2 days in 220 DEG C of baking oven；Then it is centrifuged 8 times by reactant taking-up deionized water cleaning and with 500 revs/min of rotating speed,
Finally dry the product obtaining in 100 DEG C of vacuum drying ovens.
Embodiment 3
Successively by reactant presoma 40ml deionized water, 40mmol copper chloride, 40mmol nitric acid antimony (bismuth), 800mmol
Thioacetamide, 30g potassium hydroxide add in the reactor of 100ml, stir 18min at ambient temperature, then by reactor
Put into after sealing in 240 DEG C of baking oven and react 5 days；Then reactant is taken out deionized water cleaning and with 3000 revs/min
Rotating speed is centrifuged 10 times, finally dries the product obtaining in 70 DEG C of vacuum drying ovens.
Embodiment 4
Successively by reactant presoma 30ml deionized water, 50mmol copper nitrate, 50mmol stibium oxide (bismuth), 1000mmol
Sodium sulfide, 20g potassium hydroxide add in the reactor of 80ml, stir 20min at ambient temperature, after then sealing reactor
Put in 250 DEG C of baking oven and react 1 day；Then by reactant take out deionized water cleaning and with 2000 revs/min of rotating speed from
The heart 3 times, finally dries the product obtaining in 30 DEG C of vacuum drying ovens.
Embodiment 5
Successively by reactant presoma 20ml deionized water, 15mmol copper sulfate, 15mmol antimony hydroxide (bismuth),
300mmol sodium thiosulfate, 15g potassium hydroxide add in the reactor of 30ml, stir 12min at ambient temperature, then will
React 6 days in the baking oven putting into 150 DEG C after reactor sealing；Then by reactant take out deionized water cleaning and with 700 turns/
The rotating speed dividing is centrifuged 7 times, finally dries the product obtaining in 50 DEG C of vacuum drying ovens.
Embodiment 6
Successively by reactant presoma 15ml deionized water, 25mmol Cu-lyt., 25mmol antimony (bismuth) powder, 500mmol
Thiacetic acid., 6g potassium hydroxide add in the reactor of 40ml, stir 15min at ambient temperature, then seal reactor
Put into afterwards in 180 DEG C of baking oven and react 10 days；Then reactant is taken out deionized water cleaning and with 1500 revs/min of rotating speed
Centrifugation 9 times, finally dries the product obtaining in 90 DEG C of vacuum drying ovens.
Embodiment 7
Successively by reactant presoma 25ml deionized water, 30mmol copper powder, 30mmol Butter of antimony. (bismuth), 600mmol
Thiourea, 25g potassium hydroxide add in the reactor of 30ml, stir 7min at ambient temperature, put after then sealing reactor
Enter in 160 DEG C of baking oven and react 8 days；Then reactant is taken out deionized water cleaning and with 1200 revs/min of rotating speed centrifugation 6
Secondary, in 40 DEG C of vacuum drying ovens, finally dry the product obtaining.
Embodiment 8
Successively by reactant presoma 35ml deionized water, 20mmol Schweinfurt green, 20mmol nitric acid antimony (bismuth), 400mmol
Thiourea, 10g potassium hydroxide add in the reactor of 60ml, stir 18min at ambient temperature, put after then sealing reactor
Enter in 230 DEG C of baking oven and react 4 days；Then reactant is taken out deionized water cleaning and with 2500 revs/min of rotating speed centrifugation 4
Secondary, in 60 DEG C of vacuum drying ovens, finally dry the product obtaining.
Embodiment 9
Successively by reactant presoma 12ml deionized water, 8mmol Schweinfurt green, 8mmol zinc nitrate (manganese), 26mmol sulfur
Urea, 15g potassium hydroxide add in the reactor of 40ml, stir 16min at ambient temperature, put into after then sealing reactor
React 3 days in 215 DEG C of baking oven；Then reactant is taken out deionized water cleaning and with 3200 revs/min of rotating speed centrifugation 3
Secondary, in 75 DEG C of vacuum drying ovens, finally dry the product obtaining.
Embodiment 10
Successively by reactant presoma 24ml deionized water, 16mmol silver nitrate, 8mmol germanium chloride, 45mmol thiourea,
22g potassium hydroxide adds in the reactor of 60ml, stirs 12min at ambient temperature, puts into 205 after then sealing reactor
DEG C baking oven in react 4 days；Then reactant is taken out deionized water cleaning and be centrifuged 5 times with 2800 revs/min of rotating speed,
The product obtaining is dried afterwards in 75 DEG C of vacuum drying ovens.
Embodiment 11
Successively by reactant presoma 32ml deionized water, 14mmol silver acetate, 7mmol nitric acid antimony, 32mmol thiourea,
17g potassium hydroxide adds in the reactor of 50ml, stirs 13min at ambient temperature, puts into 235 after then sealing reactor
DEG C baking oven in react 2 days；Then reactant is taken out deionized water cleaning and be centrifuged 5 times with 2100 revs/min of rotating speed,
The product obtaining is dried afterwards in 50 DEG C of vacuum drying ovens.
Embodiment 12
Successively by reactant presoma 28ml deionized water, 9mmol copper chloride, 9mmol butter of tin, 23mmol thiourea,
13g potassium hydroxide adds in the reactor of 70ml, stirs 7min at ambient temperature, puts into 245 after then sealing reactor
DEG C baking oven in react 1 day；Then reactant is taken out deionized water cleaning and be centrifuged 2 times with 1900 revs/min of rotating speed,
The product obtaining is dried afterwards in 70 DEG C of vacuum drying ovens.
Claims (7)
1. a kind of hydrothermal preparing process of the polynary photoelectricity sulfide of stratiform is it is characterised in that the change of described polynary photoelectricity sulfide
Consist of ACu2SbS3, wherein, A is any one in Li, Na, K, Rb, Cs；
Described preparation method includes：
（1）After being mixed homogeneously with excessive thiourea, AOH and water in the Cu source of stoichiometric proportion and Sb source in water heating kettle in
150～250 DEG C of hydro-thermal reactions 1～10 day；
（2）Isolate product and wash, be centrifuged, drying i.e. prepared described polynary photoelectricity sulfide.
2. preparation method according to claim 1 is it is characterised in that step（1）In, the rubbing of described Cu source and described thiourea
That ratio is 1：（2～30）.
3. preparation method according to claim 1 is it is characterised in that step（1）In, described Cu source and described AOH press every
1mmol Cu source uses the ratio mixing of 0.1～5gAOH.
4. preparation method according to claim 1 is it is characterised in that step（1）In, described Cu source and described water are pressed every
1mmol Cu source uses the ratio mixing of 0.5～5g water.
5. preparation method according to claim 1 is it is characterised in that step（1）In, the compactedness of water heating kettle is 20～
80%.
6. preparation method according to any one of claim 1 to 5 it is characterised in that described Cu source be Cu hydrochlorate,
At least one in nitrate, acetate, sulfate, oxide, hydroxide and Cu simple substance.
7. preparation method according to claim 6 is it is characterised in that described Sb source is the hydrochlorate of Sb, nitrate, acetic acid
At least one in salt, sulfate, oxide, hydroxide and Sb simple substance.
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| Amitava Choudhury, et al..Synthesis, Structures, and Properties of Layered Quaternary Chalcogenides of the General Formula ALnEQ4 (A=K,Rb;Ln=Ce,Pr,Eu;E=Si,Ge;Q=S,Se).《Zeitschrift für anorganische und allgemeine Chemie》.2006,第632卷2395-2401. * |
| Facile synthesis, magnetic, electrical and photoelectric properties of layered quaternary chalcogenides K2FeCu3Q4 (Q=S and Se);Ganghua Zhang, et al.;《CrystEngComm》;20131126;第16卷(第9期);1810-1816 * |
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